Novel liquid crystalline (LC) polyacetylene derivatives were synthesized to develop advanced LC conducting polymers with an ability of quick response to an electric field used as an external force. In practice, we synthesized ferroelectric LC conducting polymers by introducing fluorine-containing chiral LC groups into side chains of polyacetylenes. Phase transition behaviors of these polymers were examined by differential scanning calorimeter and polarizing optical microscope. Mesophases as well as higher order structures were evaluated with X-ray diffraction measurements. Two of the polymers synthesized showed twist grain boundary A (TGB(A)*) and chiral smectic C (S-C*) phases in the heating and cooling processes, Observation of the S-C* phase allows us to expect that the polymer should exhibit the ferroelectricity.